WO2006113118A1 - Composition d'hygiene personnelle structuree et multiphasee, comprenant des tensioactifs anioniques ramifies - Google Patents
Composition d'hygiene personnelle structuree et multiphasee, comprenant des tensioactifs anioniques ramifies Download PDFInfo
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- WO2006113118A1 WO2006113118A1 PCT/US2006/012402 US2006012402W WO2006113118A1 WO 2006113118 A1 WO2006113118 A1 WO 2006113118A1 US 2006012402 W US2006012402 W US 2006012402W WO 2006113118 A1 WO2006113118 A1 WO 2006113118A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/03—Liquid compositions with two or more distinct layers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/42—Amides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
Definitions
- the present invention relates to a structured multi-phase personal care composition that comprises at least one branched anionic surfactant and from 0% to 10%, by weight of the first visually distinct phase, of sodium trideceth sulfate.
- Desirable personal cleansing compositions that attempt to provide skin-conditioning benefits are known. Desirable personal cleansing compositions must meet a number of criteria. For example, in order to be acceptable to consumers, a multi-phase personal cleansing composition must exhibit good cleaning properties, must exhibit good lathering characteristics, must be mild to the skin (not cause drying or irritation) and preferably should even provide a conditioning benefit to the skin.
- compositions are aqueous systems comprising emulsified conditioning oil or other similar materials in combination with a lathering surfactant. Although these products provide both conditioning and cleansing benefits, it is often difficult to formulate a product that deposits sufficient amount of skin conditioning agents on skin during use. In order to combat emulsification of the skin conditioning agents by the cleansing surfactant, large amounts of the skin conditioning agent are added to the compositions. However, this introduces another problem associated with these cleansing and conditioning products. Raising the level of skin conditioning agent in order to achieve increased deposition negatively affects the compositions speed of lather generation, total lather volume, performance and stability.
- Some surfactants used in personal cleansing compositions such as, sodium trideceth sulfate and similarly homologous chemicals based on tridecanol, also may depress the speed of lather production, although such compositions provide relatively mild cleansing. It is believed that the high level of branching in tridecanol-based surfactants and compositions that comprise them, exhibits less flash lather as a result of their water solubility. Moreover, sodium trideceth sulfate and similar homologues based on tridecanol, are relatively costly materials, as such, the compositions do not enjoy broad commercial use.
- compositions that provide cleansing with increased lather longevity and improved lathering characteristics, and skin benefits such as silky skin feel, improved soft skin feel, and improved smooth skin feel. It is desirable to formulate compositions comprising lower levels, or even no sodium trideceth sulfate, which have the same beneficial properties as high sodium trideceth sulfate compositions.
- the present invention relates to a multi-phase personal care composition that comprises a first visually distinct phase comprising a structured surfactant component; and a second visually distinct phase.
- the structured surfactant component comprises at least one branched anionic surfactant and from 0% to 10 %, by weight of the first visually distinct phase, of sodium trideceth sulfate.
- mixtures of branched and linear anionic surfactants can provide good mildness, structure, and higher flash lather volume than compositions that comprise sodium trideceth sulfate, as the only anionic surfactant.
- Sufficient mildness can be provided by the highly branched tridecanol-based anionic surfactant complemented by high flash lather volume from linear structured surfactant components.
- These properties can be accomplished in the same composition by blending sodium trideceth sulfate with surfactants having a higher proportion of linear surfactants than sodium trideceth sulfate or by selecting surfactant which naturally have less branching than sodium trideceth sulfate.
- a preferred surfactant component comprises a substantial level of mono-methyl branched surfactants leading to structure and stability of structure.
- ambient conditions refers to surrounding conditions at one (1) atmosphere of pressure, 50% relative humidity, and 25°C.
- multi-phase as used herein, is meant that the phases of the present compositions occupy separate but distinct physical spaces inside the package in which they are stored, but are in direct contact with one another (i.e., they are not separated by a barrier and they are not emulsified or mixed to any significant degree).
- the "multi-phase" personal care compositions comprise at least two visually distinct phases which are present within the container as a visually distinct pattern. The pattern results from the combination of the "multi-phase" composition by a process herein described.
- patterns include but are not limited to the following examples: striped, marbled, rectilinear, interrupted striped, check, mottled, veined, clustered, speckled, geometric, spotted, ribbons, helical, swirl, arrayed, variegated, textured, grooved, ridged, waved, sinusoidal, spiral, twisted, curved, cycle, streaks, striated, contoured, anisotropic, laced, weave or woven, basket weave, spotted, and tessellated.
- the pattern is selected from the group consisting of striped, geometric, marbled, and combinations thereof.
- the striped pattern may be relatively uniform across the dimension of the package.
- the striped pattern may be uneven, i.e. wavy, or may be non-uniform in dimension.
- the striped pattern does not need to necessarily extend across the entire dimension of the package.
- the size of the stripes can be at least about 0.1mm in width and 10 mm in length, preferably at least about 1 mm in width and at least 20 mm in length as measured from the package exterior.
- the phases may be various different colors, and/or include particles, glitter or pearlescent agents in at least one of the phases in order to offset its appearance from the other phase(s) present.
- multi-phase personal care composition refers to compositions intended for topical application to the skin or hair.
- a phase generally occupies a space or spaces having dimensions larger than the colloidal or sub- colloidal components it comprises.
- a phase may also be constituted or re-constituted, collected, or separated into a bulk phase in order to observe its properties, e.g., by centrifugation, filtration or the like.
- compositions of the present invention preferably exhibit enhanced stability, in that the first visually distinct phase has greater than 50% Viscosity Retention measured according to the T-Bar method disclosed herein.
- structured surfactant component means the total of all anionic, nonionic, amphoteric, zwitterionic and cationic surfactants in a phase.
- water and electrolyte are excluded from the calculations involving the structured surfactant component, since surfactants as manufactured typically are diluted and neutralized.
- the term "structured,” as used herein means having a rheology that confers stability on the multi-phase composition.
- the degree of structure is determined by characteristics determined by one or more of the following methods the Yield Stress Method, or the Zero
- a surfactant phase of the multiphase composition of the present invention is considered “structured,” if the surfactant phase has one or more of the following properties described below according to the Yield Stress Method, or the Zero Shear Viscosity Method or by the Ultracentrifugation Method.
- a surfactant phase is considered to be structured, if the phase has one or more of the following characteristics:
- a Zero Shear Viscosity of at least about 500 Pascal-seconds (Pa-s), preferably at least about 1,000 Pa-s, more preferably at least about 1,500 Pa-s, even more preferably at least about 2,000 Pa-s; or C. a Structured Domain Volume Ratio as measured by the Ultracentrifugation
- the multi-phase personal care composition of the present invention is typically extrudable or dispensable from a package.
- the multi-phase personal care compositions typically exhibit a viscosity of from about 1,500 centipoise (cP) to about 1,000,000 cP, as measured by the Viscosity Method as described in copending application serial number 10/841174 filed on May 7, 2004 titled "Multi-phase Personal Care Compositions.”
- each individual phase is evaluated prior to combining, unless otherwise indicated in the individual methodology.
- each phase can be separated by centrifugation, ultracentrifugation, pipetting, filtering, washing, dilution, concentration, or combination thereof, and then the separate components or phases can be evaluated.
- the separation means is chosen so that the resulting separated components being evaluated is not destroyed, but is representative of the component as it exists in the structured multi-phase personal care composition, i.e., its composition and distribution of components therein is not substantially altered by the separation means.
- multi-phase compositions comprise domains significantly larger than colloidal dimensions so that separation of the phases into the bulk is relatively easy to accomplish while retaining the colloidal or microscopic distribution of components therein.
- the compositions of the present invention are rinse-off formulations, by which is meant the product is applied topically to the skin or hair and then subsequently (i.e., within minutes) the skin or hair is rinsed with water, or otherwise wiped off using a substrate or other suitable removal means with deposition of a portion of the composition.
- the structured multi-phase personal care composition comprises at least two visually distinct phases wherein a first phase is visually distinct from a second phase.
- the visually distinct phases are packaged in physical contact with one another and are stable.
- the visually distinct phases form a pattern. Phases:
- the multi-phase personal care compositions of the present invention comprise at least two visually distinct phases, wherein the composition can have a first phase, a second phase, a third phase, a fourth phase, and so on.
- the ratio of a first phase to a second phase is typically from about 1:99 to about 99:1, preferably from 90:10 to about 10:90, more preferably from about 80:20 to about 20:80, even more preferably about from 70:30 to about 30:70, still even more preferably about 60:40 to about 40:60, even still even more preferably about 50:50.
- the first visually distinct phase of a multi-phase personal care composition of the present invention can comprises a structured surfactant component.
- the structured surfactant component comprises at least of branched anionic surfactant and from 0 to 10% by weight of the first visually distinct phase, of sodium trideceth sulfate.
- the structured surfactant component comprises a mixture of surfactants.
- the structured multi-phased personal care composition comprises from about 1 % to about 99 %, by weight of the composition, of said first visually distinct phase.
- the structured surfactant component comprises at least one branched anionic surfactant.
- the structured surfactant component preferably comprises a lathering surfactant or a mixture of lathering surfactants.
- the structured surfactant component comprises surfactants suitable for application to the skin or hair. Suitable surfactants for use herein include any known or otherwise effective cleansing surfactant suitable for application to the skin, and which are otherwise compatible with the other essential ingredients in the structured multi-phase personal care composition including water. These surfactants include anionic, nonionic, cationic, zwitterionic, amphoteric surfactants, soap, or combinations thereof.
- anionic surfactant comprises at least 40% of the structured surfactant component, more preferably from about 45% to about 95% of the structured surfactant component, even more preferably from about 50% to about 90%, still more preferably from about 55% to about 85%, and even still most preferably at least about 60% of the structured surfactant component comprises anionic surfactant.
- the multi-phase personal care composition preferably comprises a structured surfactant component at concentrations ranging from about 2% to about 23.5%, more preferably from about 3% to about 21%, even more preferably from about 4% to about 20.4%, still more preferably from about 5% to about 20%, still even more preferably from about 13% to about 18.5%, and even still even more preferably from about 14% to about 18%, by weight of the first visually distinct phase.
- the first visually distinct phase comprising the structured surfactant component is preferably a structured domain comprising surfactants.
- the structured domain enables the incorporation of high levels of benefit components in a separate phase that are not emulsified in the composition.
- the structured domain is an opaque structured domain.
- the opaque structured domain is preferably a lamellar phase.
- the lamellar phase produces a lamellar gel network.
- the lamellar phase can provide resistance to shear, adequate yield to suspend particles and droplets and at the same time provides long term stability, since it is thermodynamically stable.
- the lamellar phase tends to have a higher viscosity thus minimizing the need for viscosity modifiers.
- the first visually distinct phase typically provides a Total Lather Volume of at least about 600 ml, preferably greater than about 800ml, more preferably greater than about 1000ml, even more preferably greater than about 1200ml, and still more preferably greater than about 1500ml, as measured by the Lather Volume Test described hereafter.
- the first visually distinct phase preferably has a Flash Lather Volume of at least about 300 ml, preferably greater than about 400ml, even more preferably greater than about 500ml, as measured by the Lather Volume Test described hereafter.
- Suitable surfactants are described in McCutcheon's, Detergents and Emulsifiers, North American edition (1986), published by allured Publishing Corporation; and McCutcheon's, Functional Materials, North American Edition (1992); and in U.S. Patent 3,929,678 issued to Laughlin, et al on December 30, 1975.
- Preferred linear anionic surfactants for use in the structured surfactant phase of the multiphase, personal care composition include ammonium lauryl sulfate, ammonium laureth sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, potassium lauryl sulfate, and combinations thereof.
- Amphoteric surfactants are suitable for use in the multiphase composition of the present invention.
- amphoteric surfactants include those that are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
- anionic water solubilizing group e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
- Examples of compounds falling within this definition are sodium 3-dodecyl-aminopropionate, sodium 3- dodecylaminopropane sulfonate, sodium lauryl sarcosinate, and N-alkyltaurines.
- Zwitterionic surfactants suitable for use include those that are broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
- Zwitterionic surfactants suitable for use in the multiphase, personal care composition include betaines, including cocoamidopropyl betaine.
- Non-limiting examples of preferred nonionic surfactants for use herein are those selected form the group consisting of glucose amides, alkyl polyglucosides, sucrose cocoate, sucrose laurate, alkanolamides, ethoxylated alcohols and mixtures thereof.
- the nonionic surfactant is selected from the group consisting of glyceryl monohydroxystearate, isosteareth-2, trideceth-3, hydroxystearic acid, propylene glycol stearate, PEG-2 stearate, sorbitan monostearate, glyceryl laurate, laureth-2, cocamide monoethanolamine, lauramide monoethanolamine, and mixtures thereof.
- anionic surfactants can be used in some embodiments, including mixtures of linear and branched surfactants, and anionic surfactants combined with nonionic, amphoteric, and/or zwitterionic surfactants.
- An electrolyte if used, can be added per se to the multiphase personal care composition or it can be formed in situ via the counterions included in one of the raw materials.
- the electrolyte preferably includes an anion comprising phosphate, chloride, sulfate or citrate and a cation comprising sodium, ammonium, potassium, magnesium or mixtures thereof.
- Some preferred electrolytes are sodium chloride, ammonium chloride, sodium or ammonium sulfate.
- the electrolyte is preferably added to the structured surfactant phase of the composition in the amount of from about 0.1% to about 15% by weight, preferably from about 1% to about 6% by weight, more preferably from about 3% to about 6%, by weight of the structured surfactant composition.
- the multiphase, personal care composition comprises a structured surfactant phase comprising a mixture of at least one nonionic surfactant, and an electrolyte.
- the surfactant phase can comprise a mixture of surfactants, water, at least one anionic surfactant, an electrolyte, and at least one alkanolamide.
- At least one anionic surfactant comprising anionic surfactant molecules of the present invention is preferably branched.
- a surfactant molecule is branched when the hydrocarbon tail of the surfactant molecule comprises at least one ternary or quaternary carbon atom, such that a methyl, ethyl, propyl, butyl, pentyl or hexyl side chain extends from the hydrocarbon backbone.
- the hydrocarbon backbone is described by the longest hydrocarbon length in the hydrocarbon tail.
- a side chain in the branched hydrocarbon of a surfactant molecule can be described by its position on the backbone, counting from the first carbon attached to a hydrophilic atom, enumerated as carbon number 1, the adjacent carbon on the backbone being carbon number 2, and so on. Side chains are also described by their length, a single carbon side chain denoted methyl; a 2-carbon length denoted ethyl, and so on. Side chains that have their own branching are denoted by conventional nomenclature techniques, e.g., isopropyl, but are less common.
- Anionic surfactant molecules which do not have branching are linear anionic surfactant molecules, and surfactants comprising a preponderance of linear anioinic surfactant molecules as indicated hereafter are linear anionic surfactants.
- anionic surfactants typically comprises a mixture of different types of surfactant molecules
- anionic surfactants can be called linear or branched depending on the relative amounts of individual surfactant molecules of different types that comprise the anionic surfactant.
- sodium tridecyl sulfate and sodium trideceth sulfate can be called branched surfactants because they typically comprise nearly all (>95%) branched surfactant molecules.
- an anionic surfactant is considered branched surfactant when at least 10% of its hydrocarbon chains are branched molecules.
- Branched anionic surfactants comprise surfactant molecules having different kinds of branching.
- Some branched anionic surfactants such as tridecanol based sulfates such as sodium trideceth sulfate, comprise a high level of branching, with over 80% of surfactant molecules comprising at least 2 branches and having an average of about 2.7 branches per molecule in some sodium trideceth sulfates.
- Other branched anionic surfactants such as C 12 - J3 alkyl sulfate derived from Safol TM 23 alcohol (Sasol, Inc, Houston, TX, USA) comprise a mixture of about 50-55% linear anionic surfactant molecules, with about 15-30% branched surfactant molecules.
- anionic surfactants comprising more than 10% branched surfactant molecules, but having an average of less than 2.0 branches per molecule, are considered monomethyl branched anionic surfactants.
- Branching information for many surfactants is typically known or obtainable from suppliers of branched alcohol feedstocks.
- Sasol publishes the following information related to Safol TM 23 primary alcohol: Linear Alcohol Isomers 50%
- Safol TM 23 alcohol can be sulfated, for example in an SO 3 /air stream falling film reactor followed by rapid neutralization with sodium hydroxide to produce sodium C 12 - 13 alkyl sulfate, a process known in the art. Since the sulfation process involves no rearrangement of the hydrocarbon backbone, the backbone of the C 12 - 13 alkyl sulfate has the same structure as the Safol TM 23 alcohol, and is a branched anionic surfactant, and is also a monomethyl branched anionic surfactant.
- Other suppliers of alcohols provide similar information on their primary alcohols, e.g., Shell Chemical for the Neodol TM primary alcohols.
- GC-MS gas chromatography - mass spectrometry
- a typical GC program is 80-320C at 5C/min rate on a 30 m x 0.25 mm DB-I (0.25 uM film) column, and can give specific information on branching location for a majority of a hydrocarbon tail of an anionic surfactant.
- GC-MS is able to obtain the amount of branched components, which is taken as 100% minus the sum of n- C12 and «-C13 eluted.
- n-C ⁇ , n-C ⁇ 2 and W-C 13 elution times are known for a column and/or can be obtained by simple running of standards which are available.
- inventors sum all oxazoline peaks in the GC window between n ⁇ C ⁇ ⁇ and H-C 12 , said peaks are the branched Cj 2 peaks; sum all oxazoline peaks in the GC window between n-Cn and W-C 13 , said peaks are the branched Cj 3 peaks; dividing the peak areas obtained by the total area obtained, including linear C 12 and linear C 13 , to obtain the fractional amount of each component.
- the sum of the peak fractions in the branched C 12 and branched C 13 windows, added together, is the fraction of branched molecules, which can be expressed as a percentage.
- the integrated area under each GC peak is the peak information used in the calculations.
- the surfactant can even be obtained by extraction from a composition first, e.g. by filtration such as cross flow filtration. From the GC data, the number of branch points per hydrocarbon chain is summed, multiplying number of branches per molecule by mole fraction for each species identified to obtain an average degree of branching per molecule for the surfactant. For example, 50% of molecules having 1 branch point with 50% linear molecules is an average degree of branching of 0.5.
- Branched anionic surfactants include but are not limited to the following surfactants: sodium trideceth sulfate, sodium tridecyl sulfate, sodium C 12 - 13 alkyl sulfate, sodium C 12-15 alkyl sulfate, sodium Cn- J5 alkyl sulfate, sodium C 12 - 18 alkyl sulfate, sodium C 10 - 16 alkyl sulfate, sodium C 12 - 13 pareth sulfate, sodium C 12 - J3 pareth- « sulfate, and sodium C 12 - 14 pareth-r ⁇ sulfate.
- alkoxylates include the ethylene oxide, propylene oxide and EO/PO mixed alkoxylates. Phosphates, carboxylates and sulfonates prepared from branched alcohols are also useful anionic branched surfactants.
- Branched surfactants can be derived from synthetic alcohols such as the primary alcohols from the liquid hydrocarbons produced by Fischer-Tropsch condensed syngas, for example Safol TM 23 Alcohol available from Sasol North America, Houston, TX; from synthetic alcohols such as Neodol TM 23 Alcohol available from Shell Chemicals, USA; from synthetically made alcohols such as those described in U.S. Patent No. 6,335,312 issued to Coffindaffer, et al on January 1, 2002.
- Preferred alcohols are Safol TM 23 and Neodol TM 23.
- Preferred alkoxylated alcohols are Safol TM 23-3 and Neodol TM 23-3.
- Sulfates can be prepared by conventional processes to high purity from a sulfur based SO 3 air stream process, chlorosulfonic acid process, sulfuric acid process, or Oleum process. Preparation via SO 3 air stream in a falling film reactor is a preferred sulfation process.
- Monomethyl branched anionic surfactants include but are not limited to the branched anionic sulfates derived from Safol TM 23- « and Neodol TM 23-n as previously described, where n is an integer between 1 and about 20.
- Fractional alkloxylation is also useful, for example by stoichiometrically adding only about 0.3 moles EO, or 1.5 moles EO, or 2.2 moles EO, based on the moles of alcohol present, since the molecular combinations that result are in fact always distributions of alkoxylates so that representation of n as an integer is merely an average representation.
- Preferred monomethyl branched anionic surfactants include a Ci 2 - I3 alkyl sulfate derived from the sulfation of Safol TM 23, which has about 28% branched anionic surfactant molecules; and a C12-13 pareth sulfate derived from Neodol TM 23-3, which has about 10-18% branched anionic surfactant molecules.
- the anionic surfactant when it is a branched anionic primary sulfate, it may contain some of the following branched anionic surfactant molecules: 4-methyl undecyl sulfate, 5-methyl undecyl sulfate, 7-methyl undecyl sulfate, 8-methyl undecyl sulfate, 7-methyl dodecyl sulfate, 8-methyl-dodecyl sulfate, 9-methyl dodecyl sulfate, 4,5-dimethyl decyl sulfate, 6,9-dimethyl decyl sulfate, 6,9-dimethyl undecyl sulfate, 5-methyl-8-ethyl undecyl sulfate, 9-methyl undecyl sulfate, 5,6,8-trimethyl decyl sulfate, 2-methyl dodecyl sulfate, and 2-methyl undecyl sulfate
- the anionic surfactant is a primary alkoxylated sulfate
- the second visually distinct phase is distinguishable from the first visually distinct phase by having a different color, opacity may comprise a structured surfactant or a non- lathering structured Aqueous Phase.
- the second visually distinct phase may comprise a structured surfactant identical to the structured surfactant in the first visually distinct phase; described in detail above.
- the second visually distinct phase of the multi-phase personal care compositions of the present invention can comprise a structured aqueous phase that comprises a water structurant and water.
- the structured aqueous phase can be hydrophilic and in a preferred embodiment the structured aqueous phase is a hydrophilic, non-lathering gelled water phase.
- the structured aqueous phase typically comprises less than about 5%, preferably less than about 3%, and more preferably less than about 1%, by weight of the structured aqueous phase, of a surfactant.
- the structured aqueous phase is free of lathering surfactant in the formulation.
- a preferred structured aqueous phase is a non-lathering structured aqueous phase as described in published U.S. Patent Application No. 2005/0143269A1 entitled "Multiphase Personal Cleansing Compositions Containing A Lathering Cleansing Phase And A Non-Lathering Structured Aqueous Phase.”
- the structured aqueous phase of the present invention can comprise from about 30% to about 99%, by weight of the structured aqueous phase, of water.
- the structured aqueous phase generally comprises more than about 50%, preferably more than about 60%, even more preferably more than about 70%, and still more preferably more than about 80%, by weight of the structured aqueous phase, of water.
- the structured aqueous phase will typically have a pH of from about 5 to about
- a water structurant for the structured aqueous phase can have a net cationic charge, net anionic charge, or neutral charge.
- the structured aqueous phase of the present compositions can further comprise optional ingredients such as, pigments, pH regulators (e.g. triethanolamine), and preservatives.
- the structured aqueous phase can comprise from about 0.1% to about 30%, preferably from about 0.5% to about 20%, more preferably from about 0.5% to about 10%, and even more preferably from about 0.5% to about 5%, by weight of the structured aqueous phase, of a water structurant.
- the water structurant is typically selected from the group consisting of inorganic water structurants, charged polymeric water structurants, water soluble polymeric structurants, associative water structurants, and mixtures thereof.
- inorganic water structurants include silicas, polymeric gellants such as polyacrylates, polyacrylamides, starches, modified starches, crosslinked polymeric gellants, copolymers, and mixtures thereof.
- Non-limiting examples of charged polymeric water structurants for use in the multi-phase personal care composition include Acrylates/Vinyl Isodecanoate Crosspolymer (Stabylen 30 from 3V), Acrylates/C 10-30 Alkyl Acrylate Crosspolymer (Pemulen TRl and TR2), Carbomers, Ammonium Acryloyldimethyltaurate/VP Copolymer (Aristoflex AVC from Clariant), Ammonium Acryloyldimethyltaurate/Beheneth-25 Methacrylate Crosspolymer (Aristoflex HMB from Clariant), Acrylates/Ceteth-20 Itaconate Copolymer (Structure 3001 from National Starch), Polyacrylamide (Sepigel 305 from SEPPIC), and mixtures thereof.
- Acrylates/Vinyl Isodecanoate Crosspolymer (Stabylen 30 from 3V)
- Non-limiting examples of water soluble polymeric structurants for use in the multi-phase personal care composition include cellulose gums and gel, and starches.
- Non-limiting examples of associative water structurants for use in the multi-phase personal care composition include xanthum gum, gellum gum, pectins, alginates such as propylene glycol alginate, and mixtures thereof. Additional Ingredients:
- the phases of the multi-phase personal care composition can further comprise a polymeric phase structurant.
- the compositions of the present invention typically can comprise from about 0.05% to about 10%, preferably from about 0.1% to about 4%, of a polymeric phase structurant.
- polymeric phase structurant include but are not limited to the following examples: naturally derived polymers, synthetic polymers, crosslinked polymers, block copolymers, copolymers, hydrophilic polymers, nonionic polymers, anionic polymers, hydrophobic polymers, hydrophobically modified polymers, associative polymers, and oligomers.
- the polymeric phase structurant can be crosslinked and further comprise a crosslinking.
- These polymeric phase structurant useful in the present invention are more fully described in U.S. Pat. No. 5,087,445, to Haffey et al., issued Feb. 11, 1992; U.S. Pat. No. 4,509,949, to Huang et al., issued Apr. 5, 1985, U.S. Pat. No. 2,798,053, to Brown, issued JuI. 2, 1957. See also, CTFA International Cosmetic Ingredient Dictionary, fourth edition, 1991, pp. 12 and 80.
- the phase of the present compositions optionally can further comprise a liquid crystalline phase inducing structurant, which when present is at concentrations ranging from about 0.3% to about 15%, by weight of the phase, more preferably at from about 0.5% to about 5% by weight of the phase.
- suitable liquid crystalline phase inducing structurants include fatty acids (e.g. lauric acid, oleic acid, isostearic acid, linoleic acid) ester derivatives of fatty acids (e.g. propylene glycol isostearate, propylene glycol oleate, glyceryl isostearate) fatty alcohols, trihydroxystearin (available from Rheox, Inc. under the trade name THIXCIN ® R).
- the liquid crystalline phase inducing structurant is selected from lauric acid, trihydroxystearin, lauryl pyrrolidone, and tridecanol.
- the structured multi-phase personal care compositions of the present invention can additionally comprise an organic cationic deposition polymer in the one or more phases as a deposition aid for the benefit agents described herein.
- Suitable cationic deposition polymers for use in the structured multi-phase personal care compositions of the present invention contain cationic nitrogen-containing moieties such as quaternary ammonium or cationic protonated amino moieties.
- the cationic protonated amines can be primary, secondary, or tertiary amines (preferably secondary or tertiary), depending upon the particular species and the selected pH of the structured multi-phase personal care composition.
- Suitable cationic deposition polymers that would be useful in the compositions of the present invention are disclosed in the co-pending and commonly assigned U.S. Patent Application No. 60/628,036 filed on November 15, 2003 by Wagner, et al titled "Depositable Solids.”
- One or more of the phases of the multiphase personal care composition can comprise a variety of additional optional ingredients such as shiny particles, beads, exfoliating beads.
- additional optional ingredients are most typically those materials approved for use in cosmetics and that are described in reference books such as the CTFA Cosmetic Ingredient Handbook, Second Edition, The Cosmetic, Toiletries, and Fragrance Association, Inc. 1988, 1992.
- vitamins and derivatives thereof e.g., ascorbic acid, vitamin E, tocopheryl acetate, and the like
- sunscreens e.g., thickening agents, preservatives for maintaining the anti microbial integrity of the cleansing compositions, anti-acne medicaments, antioxidants, skin soothing and healing agents such as aloe vera extract, allantoin and the like, chelators and sequestrants, skin lightening agents, and agents suitable for aesthetic purposes such as fragrances, essential oils, skin sensates, pigments, pearlescent agents and essential oils and fragrance.
- the preferred pH range of the structured multi-phase personal care composition is from about 5 to about 8.
- Test Methods Yield Stress and Zero Shear Viscosity Method: The Yield Stress and Zero Shear Viscosity of a phase of the present composition, can be measured either prior to combining in the composition, or after combining in the composition by separating the phase by suitable physical separation means, such as centrifugation, pipetting, cutting away mechanically, rinsing, filtering, or other separation means.
- a controlled stress rheometer such as a TA Instruments AR2000 Rheometer is used to determine the Yield Stress and Zero Shear Viscosity. The determination is performed at 25 0 C with the 4 cm diameter parallel plate measuring system and a 1 mm gap.
- the geometry has a shear stress factor of 79580 m '3 to convert torque obtained to stress.
- phase is obtained and placed in position on the rheometer base plate, the measurement geometry (upper plate) moving into position 1 mm above the base plate. Excess phase at the geometry edge is removed by scraping after locking the geometry. If the phase comprises particles discernible to the eye or by feel (beads, e.g.) which are larger than about 150 microns in number average diameter, the gap setting between the base plate and upper plate is increased to the smaller of 4 mm or 8-fold the diameter of the 95 th volume percentile particle diameter. If a phase has any particle larger than 5 mm in any dimension, the particles are removed prior to the measurement.
- the determination is performed via the programmed application of a continuous shear stress ramp from 0.1 Pa to 1,000 Pa over a time interval of 5 minutes using a logarithmic progression, i.e., measurement points evenly spaced on a logarithmic scale. Thirty (30) measurement points per decade of stress increase are obtained. Stress, strain and viscosity are recorded. If the measurement result is incomplete, for example if material flows from the gap, results obtained are evaluated and incomplete data points excluded.
- the Yield Stress is determined as follows. Stress (Pa) and strain (unitless) data are transformed by taking their logarithms (base 10). Log(stress) is graphed vs. log(strain) for only the data obtained between a stress of 0.2 Pa and 2.0 Pa, about 30 points.
- the Yield Stress is the first stress (Pa) at which %variation exceeds 10% and subsequent (higher) stresses result in even greater variation than 10% due to the onset of flow or deformation of the structure.
- the Zero Shear Viscosity is obtained by taking a first median value of viscosity in Pascal-seconds (Pa-sec) for viscosity data obtained between and including 0.1 Pa and the Yield Stress. After taking the first median viscosity, all viscosity values greater than 5-fold the first median value and less than 0.2x the median value are excluded, and a second median viscosity value is obtained of the same viscosity data, excluding the indicated data points. The second median viscosity so obtained is the Zero Shear Viscosity.
- Lather volume of a first visually distinct phase, a structured surfactant component or a structured domain of a structured multi-phase personal care composition is measured using a graduated cylinder and a rotating apparatus.
- a 1,000 ml graduated cylinder is used which is marked in 10 ml increments and has a height of 14.5 inches at the 1,000 ml mark from the inside of its base (for example, Pyrex No. 2982).
- Distilled water 100 grams at 25°C is added to the graduated cylinder.
- the cylinder is clamped in a rotating device, which clamps the cylinder with an axis of rotation that transects the center of the graduated cylinder.
- the first lather volume the lowest height at which it is possible to see halfway across the graduated cylinder. If the lather is so coarse that a single or only a few foam cells which comprise the lather ("bubbles") reach across the entire cylinder, the height at which at least 10 foam cells are required to fill the space is the first lather volume, also in ml up from the base. Foam cells larger than one inch in any dimension, no matter where they occur, are designated as unfilled air instead of lather.
- Foam that collects on the top of the graduated cylinder but does not drain is also incorporated in the measurement if the foam on the top is in its own continuous layer, by adding the ml of foam collected there using a ruler to measure thickness of the layer, to the ml of foam measured up from the base.
- the maximum lather height is 1,000 ml (even if the total lather height exceeds the 1,000 ml mark on the graduated cylinder).
- a second rotation sequence is commenced which is identical in speed and duration to the first rotation sequence.
- the second lather volume is recorded in the same manner as the first, after the same 15 seconds of drainage time.
- a third sequence is completed and the third lather volume is measured in the same manner, with the same pause between each for drainage and taking the measurement.
- compositions according to the present invention perform significantly better in this test than similar compositions in conventional emulsion form.
- the Ultracentrifugation Method is used to determine the percent of a structured domain or an opaque structured domain that is present in a structured multi-phase personal care composition that comprises a first visually distinct phase comprising a structured surfactant component.
- the method involves the separation of the composition by ultracentrifugation into separate but distinguishable layers.
- the structured multi-phase personal care composition of the present invention can have multiple distinguishable layers, for example a non-structured surfactant layer, a structured surfactant layer, and a benefit layer.
- the relative phase volume by measuring the height of each layer visually using an Electronic Digital Caliper (within 0.01mm).
- H 8 the total height
- H b the height of the benefit layer
- H c the structured surfactant layer
- the benefit layer is determined by its low moisture content (less than 10% water as measured by Karl Fischer Titration). It generally presents at the top of the centrifuge tube.
- the total surfactant layer height (H s ) can be calculated by this equation:
- the structured surfactant layer components may comprise several layers or a single layer.
- This clear isotropic layer typically represents the non-structured micellar surfactant layer.
- the layers above the isotropic phase generally comprise higher surfactant concentration with higher ordered structures (such as liquid crystals). These structured layers are sometimes opaque to naked eyes, or translucent, or clear. There is generally a distinct phase boundary between the structured layer and the non-structured isotropic layer.
- the physical nature of the structured surfactant layers can be determined through microscopy under polarized light.
- the structured surfactant layers typically exhibit distinctive texture under polarized light.
- Structured surfactant layer display multiple lines that are often associated primarily with the long spacings of the liquid crystal structure. There may be several structured layers present, so that H 0 is the sum of the individual structured layers. If a coacervate phase or any type of polymer-surfactant phase is present, it is considered a structured phase.
- H 5 H 3 .
- T- Bar Method for Assessing Structured Surfactant Stability In Presence of Lipid The stability of a surfactant-containing phase ("cleansing phase" or "first visually distinct phase") in the presence of lipid can be assessed using a T-Bar Viscosity Method.
- the apparatus for T-Bar measurement includes a Brookfield DV-II+ Pro Viscometer with Helipath Accessory; chuck, weight and closer assembly for T-bar attachment; a T-bar Spindle D, a personal computer with Rheocalc software from Brookfield, and a cable connecting the Brookfield Viscometer to the computer. First, weigh 40 grams of the cleansing phase in a 4-oz glass jar.
- the initial T-Bar viscosity " Tj n i , " is the average T-Bar viscosity reading between the 6 th reading and the 35 th reading (the first five and the last five readings are not used for the average T-Bar viscosity calculation).
- Prepare a separate lipid blend by heating a vessel to 180 0 F (82.2°C) and add together 70 parts of Petrolatum (G2218 from WITCO) and 30 parts of Hydrobrite 1000 White Mineral Oil. Cool the vessel to HO 0 F (43.3 0 C )with slow agitation (200rpm). Stop agitation and cool the vessel to ambient temperature overnight.
- a stable cleansing phase exhibits a uniform layer at the bottom of the jar, below the less dense petrolatum/oil phase.
- An unstable cleansing phase can form layers not present in the originally centrifuged cleansing phase (i.e., an isotropic phase) either at the bottom or between the cleansing phase-lipid interface. If more than one layer is present in the cleansing phase, measure the height of each newly formed layer, "H ne w" using an Electronic Caliper. Add together the heights of all the newly formed layers.
- the new phase volume ratio is calculated as H new /H S urf *100% ,using the height of all new layers added together as H new
- a stable structured cleansing phase forms less than 10% of new phase volume. More preferably, a stable structured cleansing phase forms less than 5% of new phase volume. Most preferably, a stable structured cleansing phase forms 0% of new phase volume.
- the T-Bar viscosity of the centrifuged contents of the jar is then measured using the T-Bar method above. Open the Rheocalc software and set the following data acquisition parameters: set Speed to 5rpm, set Time Wait for Torque to 00:01 (1 second), set Loop Start Count at 80. Start the data acquisition and turn on the Helipath stand to travel upward at a speed of 22mm/min. There is usually a distinctive viscosity jump between the first visually distinct phase layer and the lipid layer.
- the average cleansing phase T-Bar viscosity after lipid exposure, "T aft " is the average reading between the 6 th T- Bar viscosity and the last T-Bar viscosity reading before the jump in viscosity due to the lipid layer.
- a stable structured cleansing phase has T aft higher than 10,000 cP. More preferably, a stable structured cleansing phase has T af t higher than 15,000 cP. Most preferably, a stable structured first visually distinct phase has T aft higher than 20,000 cP
- Viscosity Retention is calculated as T aft /Tj n i*100%.
- a stable structured cleansing phase has >50% Viscosity Retention. More preferably, a stable structured cleansing phase has >70% Viscosity Retention. . Most preferably, a stable structured cleansing phase has >80% Viscosity Retention.
- the multi-phase personal care compositions of the present invention are preferably applied topically to the desired area of the skin or hair in an amount sufficient to provide effective delivery of the skin cleansing agent, hydrophobic material, and particles to the applied surface.
- the compositions can be applied directly to the skin or indirectly via the use of a cleansing puff, washcloth, sponge or other implement.
- the compositions are preferably diluted with water prior to, during, or after topical application, and then subsequently the skin or hair rinsed or wiped off, preferably rinsed off of the applied surface using water or a water-insoluble substrate in combination with water.
- the present invention is therefore also directed to methods of cleansing the skin through the above-described application of the compositions of the present invention.
- the methods of the present invention are also directed to a method of providing effective delivery of the desired skin active agent, and the resulting benefits from such effective delivery as described herein, to the applied surface through the above-described application of the compositions of the present invention.
- the multi-phase personal care compositions of the present invention may be prepared by any known or otherwise effective technique, suitable for making and formulating the desired multi-phase product form. It is effective to combine toothpaste-tube filling technology with a spinning stage design. Additionally, the present invention can be prepared by the method and apparatus as disclosed in U.S. Patent No. 6,213,166 issued to Thibiant, et al on April 10, 2001.
- the method and apparatus allows two or more compositions to be filled with a spiral configuration into a single container. The method requires that at least two nozzles be employed to fill the container. The container is placed on a static mixer and spun as the composition is introduced into the container. Alternatively, it is effective to combine at least two phases by first placing the separate compositions in separate storage tanks having a pump and a hose attached.
- the phases are then pumped in predetermined amounts into a single combining section.
- the phases are moved from the combining sections into the blending sections and the phases are mixed in the blending section such that the single resulting product exhibits a distinct pattern of the phases.
- the pattern is selected from the group consisting of striped, marbled, geometric, and mixtures thereof.
- the next step involves pumping the product that was mixed in the blending section via a hose into a single nozzle, then placing the nozzle into a container and filing the container with the resulting product.
- the multi-phase personal care compositions are patterned, it can be desirable to be packaged as a personal care article.
- the personal care article would comprise these compositions in a transparent or translucent package such that the consumer can view the pattern through the package. Because of the viscosity of the subject compositions it may also be desirable to include instructions to the consumer to store the package upside down, on its cap to facilitate dispensing.
- every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification includes every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
- first visually distinct phases are prepared as non-limiting examples (chemical content is shown).
- Examples 1 and 2 are Comparative Examples of the first visually distinct phase of the present invention.
- Examples 3-7 are examples of the first visually distinct phase of the present invention.
- Examples 8, 9 and 10 are Comparative Examples.
- Examples 11 and 12 are examples of structured aqueous phase of the present invention.
- Examples 1 and 2 are comparative examples of the first visually distinct phase of the present invention which comprise all linear anionic surfactants.
- Examples 3-5 are examples of the present invention comprising a mix of linear and branched anionic surfactants. Of the mixed anionic surfactant compositions Examples 3-5, compositions with lower sodium trideceth sulfate exhibited higher flash and total lather volumes.
- Examples 8-10 are Comparative Examples.
- Example 8 does not comprise branched anionic surfactants.
- Comparative Examples 9 and 10 comprise higher sodium trideceth sulfate than in the claimed range.
- Comparative Example 8, which does not have any branched surfactants, is not stable, and also does not have lather volumes as high as Examples 6 and 7, which have both branched and linear anionic surfactants.
- the first visually distinct phase can be prepared by conventional mixing techniques. Prepare the first visually distinct phase by first adding the water, skin benefit components and thickeners into a vessel, agitating until a dispersion is formed. Then add in the following sequence: surfactants, Disodium EDTA, preservative, half the sodium chloride and all other minors except fragrance and the withheld sodium chloride. Heat to 65-70°C if Cocamide monoethanolamine is used, otherwise maintain at ambient temperature while agitating the mixing vessel. Cool to 45C if heating was used.
- gas filled microspheres having a density of about 30 kg/m 3 such as Expancel 091 DE 40 d30 (from Expancel, Inc.) can optionally be used at about 0.1-0.5 % of the batch.
- Expancel 091 DE 40 d30 from Expancel, Inc.
- a separate vessel prewet the structuring polymers with fragrance and add to the mix vessel at the same time as the remaining sodium chloride while agitating. Agitate until homogeneous, then pump through a static mixing element to disperse any lumps to complete the batch.
- the Structured Aqueous Phase of Examples 11-12 can be prepared by dispersing polymers in water with high shear, adding salt and remaining ingredients except petrolatum and mineral oil, neutralizing to pH 7.0 with triethanolamine (approximate TEA level is shown), heating to 50°C, adding the petrolatum and mineral oil as a liquid at 80 0 C, and agitating until homogeneous without high shear. Pigments having no water soluble components are preferably used. A particle size of about 5-100 microns for the petrolatum component is obtained for most of the particles.
- Visually distinct compositions are prepared by first preparing two compositions that differ in appearance.
- a first visually distinct phases of Examples 3-7 is selected (any can be selected) and pigmented using a hydrophobic pigment, which keeps color from leaching.
- a second first visually distinct phase of Examples 3-7 and 11-12 can be selected and either pigmented to a different color, pigmented white, or not pigmented, such that the phase visually differs from the first phase chosen, including by being, e.g., a transparent gel.
- the phases are added to separate hoppers and gravity fed to a package (e.g., bottle, tube, etc.) filling operation.
- the phases are maintained at ambient temperature and are simultaneously pumped in a specified volumetric ratio through 3 A in.
- One or both of the phases can be a benefit phase, or a combined benefit phase, by preparing an emulsion or a dispersion with the phase using conventional techniques to prepare an emulsion or dispersion with a dispersed phase such as petrolatum, mineral oil, other synthetic and natural oils such as jojoba, shea butter, triglyceride, lanolin, ethers, esters including emollient sucrose esters, ethers, waxes, silicone fluids, polymers including polymeric esters such as polyglyceryl esters, mixtures and combinations of these and other hydrophobic materials having a Vaughn Solubility Parameter less than about 13 (cal/cm 3 ) 1/2 .
- a dispersed phase such as petrolatum, mineral oil, other synthetic and natural oils such as jojoba, shea butter, triglyceride, lanolin, ethers, esters including emollient sucrose esters, ethers, waxes, silicone fluids, polymers including
- any of the Examples 3-7 can be diluted to a lower surfactant concentration, e.g. to 10%, or 6%, or 4% or even less than 1% surfactant so long as the phase remains continuously hydrophilic and the rheology of the phase sufficient so the visually distinct composition remains stable.
- the hydrophobic material can also be dispersed in a non-lathering structured aqueous phase, for example the non-lathering structured aqueous phase of Examples 11 or 12, as shown.
- the benefit phase can thus be lathering, or non-lathering. If the surfactant level is reduced in one of the phases, rheology can be adjusted using traditional thickeners, for example water soluble polymers, cross-linked water swellable polymers, clays, gel networks, etc., as is known to one with ordinary skill in the art.
- surfactant can be concentrated in one of the phases by reducing water content, so that the surfactant concentration is 24%, 30%, 40%, 50% or even as high as 75% of one or more of the phases in order to deliver efficient cleansing from a low level of a concentrated surfactant phase.
- levels of electrolyte (e.g., salt), thickeners and cationic polymer would be adjusted for viscosity control.
- the Zero Shear Viscosity is greater than 15,000 Pa-sec, even greater than 25,000 Pa-sec, or even greater than 35,000 Pa-sec in order to provide phases which are visually distinct and paste-like, such as for example visually distinct concentrates packaged in tubes, filled by apparati such as multi-phase toothpaste filling equipment.
- the present invention can be prepared by the method and apparatus as disclosed in U.S. Patent No. 6,213,166 issued to Thibiant et, al. on April 10, 2001 which method and apparatus allows compositions to be filled with a spiral configuration into a single container using at least 2 nozzles.
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Abstract
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MX2007012898A MX2007012898A (es) | 2005-04-13 | 2006-03-31 | Composicion de fases multiples estructurada para el cuidado personal que comprende surfactantes anionicos ramificados. |
| EP06749196A EP1874409A1 (fr) | 2005-04-13 | 2006-03-31 | Composition d'hygiene personnelle structuree et multiphasee, comprenant des tensioactifs anioniques ramifies |
| JP2008506506A JP2008538360A (ja) | 2005-04-13 | 2006-03-31 | 分枝状アニオン性界面活性剤を含む構造化された多相パーソナルケア組成物 |
| CA002603299A CA2603299A1 (fr) | 2005-04-13 | 2006-03-31 | Composition d'hygiene personnelle structuree et multiphasee, comprenant des tensioactifs anioniques ramifies |
Applications Claiming Priority (6)
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|---|---|---|---|
| US67078505P | 2005-04-13 | 2005-04-13 | |
| US60/670,785 | 2005-04-13 | ||
| US68011405P | 2005-05-12 | 2005-05-12 | |
| US68014905P | 2005-05-12 | 2005-05-12 | |
| US60/680,149 | 2005-05-12 | ||
| US60/680,114 | 2005-05-12 |
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| Publication Number | Publication Date |
|---|---|
| WO2006113118A1 true WO2006113118A1 (fr) | 2006-10-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/US2006/012402 Ceased WO2006113118A1 (fr) | 2005-04-13 | 2006-03-31 | Composition d'hygiene personnelle structuree et multiphasee, comprenant des tensioactifs anioniques ramifies |
| PCT/US2006/012401 Ceased WO2006113117A1 (fr) | 2005-04-13 | 2006-03-31 | Compositions de nettoyage pour l'hygiene personnelle douces, structurees et multiphasees |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/US2006/012401 Ceased WO2006113117A1 (fr) | 2005-04-13 | 2006-03-31 | Compositions de nettoyage pour l'hygiene personnelle douces, structurees et multiphasees |
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| US (3) | US20060276357A1 (fr) |
| EP (2) | EP1874408A1 (fr) |
| JP (1) | JP2008538360A (fr) |
| CA (1) | CA2603299A1 (fr) |
| MX (2) | MX2007012898A (fr) |
| WO (2) | WO2006113118A1 (fr) |
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2006
- 2006-03-31 JP JP2008506506A patent/JP2008538360A/ja active Pending
- 2006-03-31 EP EP06749195A patent/EP1874408A1/fr not_active Withdrawn
- 2006-03-31 WO PCT/US2006/012402 patent/WO2006113118A1/fr not_active Ceased
- 2006-03-31 MX MX2007012898A patent/MX2007012898A/es not_active Application Discontinuation
- 2006-03-31 EP EP06749196A patent/EP1874409A1/fr not_active Withdrawn
- 2006-03-31 MX MX2007007312A patent/MX2007007312A/es active IP Right Grant
- 2006-03-31 WO PCT/US2006/012401 patent/WO2006113117A1/fr not_active Ceased
- 2006-03-31 CA CA002603299A patent/CA2603299A1/fr not_active Abandoned
- 2006-04-07 US US11/400,359 patent/US20060276357A1/en not_active Abandoned
- 2006-04-07 US US11/400,634 patent/US8084407B2/en not_active Expired - Fee Related
- 2006-06-16 US US11/454,809 patent/US20070155637A1/en not_active Abandoned
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| TWI562670B (en) * | 2014-01-21 | 2016-12-11 | Alcatel Lucent | Apparatuses, methods and computer programs for a base station transceiver and a mobile transceiver |
Also Published As
| Publication number | Publication date |
|---|---|
| US20060276357A1 (en) | 2006-12-07 |
| EP1874408A1 (fr) | 2008-01-09 |
| JP2008538360A (ja) | 2008-10-23 |
| MX2007012898A (es) | 2007-12-10 |
| CA2603299A1 (fr) | 2006-10-26 |
| MX2007007312A (es) | 2007-07-09 |
| US20070155637A1 (en) | 2007-07-05 |
| US20060252662A1 (en) | 2006-11-09 |
| EP1874409A1 (fr) | 2008-01-09 |
| WO2006113117A1 (fr) | 2006-10-26 |
| US8084407B2 (en) | 2011-12-27 |
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